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CN1289055C - Cationic direct dye and direct-dyeing polymer composition used for dyeing keratin-fiber - Google Patents

Cationic direct dye and direct-dyeing polymer composition used for dyeing keratin-fiber Download PDF

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CN1289055C
CN1289055C CNB991073053A CN99107305A CN1289055C CN 1289055 C CN1289055 C CN 1289055C CN B991073053 A CNB991073053 A CN B991073053A CN 99107305 A CN99107305 A CN 99107305A CN 1289055 C CN1289055 C CN 1289055C
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dyeing
composition
group
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CN1233466A (en
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C·龙多
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LOreal SA
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B44/00—Azo dyes containing onium groups
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
    • A61K8/4926—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having six membered rings
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A61K8/4946—Imidazoles or their condensed derivatives, e.g. benzimidazoles
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A61K8/496—Triazoles or their condensed derivatives, e.g. benzotriazoles
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A61K8/4966—Triazines or their condensed derivatives
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A61Q5/065—Preparations for temporary colouring the hair, e.g. direct dyes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/10—Preparations for permanently dyeing the hair
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/42—Colour properties
    • A61K2800/43—Pigments; Dyes
    • A61K2800/432—Direct dyes
    • A61K2800/4322—Direct dyes in preparations for temporarily coloring the hair further containing an oxidizing agent

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • General Health & Medical Sciences (AREA)
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  • Veterinary Medicine (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Cosmetics (AREA)
  • Coloring (AREA)

Abstract

本发明涉及一种用于角质纤维，尤其是人体角质纤维，如毛发的染色组合物，其中在适用于染色的介质中含有至少一种已知其化学式的阳离子型直接染料，其特征在于其中还含有至少一种特定的阳离子型或两性直染聚合物。本发明还涉及使用该组合物实施染色的方法与装置。The present invention relates to a dyeing composition for keratinous fibres, especially human keratinous fibres, such as hair, comprising at least one cationic direct dye of known chemical formula in a medium suitable for dyeing, characterized in that Contains at least one specific cationic or amphoteric substantive polymer. The invention also relates to methods and devices for dyeing using the composition.

Description

The compositions of used cation direct dye of dyeing keratinous fibres and straight dyeing polymer
The present invention relates to a kind of cutin or keratin fiber of being used for, especially human cutin fibre, colouring compositions as hair, the cationic type direct dye that wherein contains at least a known its chemical formula in being applicable to painted medium is characterized in that it also contains straight (connecing) dyeing polymer of at least a specific cationic or both sexes.
The invention still further relates to and use said composition to implement painted method and apparatus.
In the field of hair, can distinguish the different dyeing of two classes.
First kind of dyeing is semipermanent or temporary transient dyeing, or direct staining, and this dyeing needs some can make the variable color more or less of self-colored hair, again can the anti-significantly repeatedly dyestuff of hair washing.This class dyestuff is called as direct dyes; This dyestuff can use separately or use with oxidant.When using oxidant, its objective is to obtain light color.The mixture of the instant preparation of direct dyes and oxidant is coated on the hair and obtains this light color, particularly by desalinating the melanin of hair, obtain ideal effect, for example when handling achromachia, obtain solid color, perhaps make the color development of Natural color hair more remarkable.
Second kind of dyeing is permanent or oxidising dyeing.It is to realize by the what is called of precursor that contains oxidation dye and colour former " oxidation " dyestuff.This oxidation dye precursors is commonly called " oxidation base material ", is colourless originally or the chemical compound of color slightly, in use, because the effect of the oxidant that is added demonstrates the dyeing function in hair, forms colouring cpd and dyestuff.The formation of this colouring cpd and dyestuff comes from " oxidation base material " oxidative condensation effect own, perhaps come from " oxidation base material " and be commonly called the oxidative condensation effect of the toner compounds of " colour former ", when these colour formers are present in oxidising dyeing usually in the used staining components.
In order to change the formed tone of above-mentioned oxidation dye, or make it be rich in gloss, add some direct dyess to it sometimes.
Cationic type direct dye commonly used in cutin, especially the human cutin fibre field comprises some chemical compounds that its structure has been put down in writing in the following document of this paper; Yet the formed tone characteristic of these dyestuffs but enough or does not make into satisfaction.On the one hand, the lack of homogeneity of whole fibre staining (same colourity), it is strong excessively to be referred to as painted selectivity, on the other hand, it is relatively poor color fastness, in other words, hair may be subjected to the influence of various external environment (light, weather is not normal, shampoo) and anti-patience is relatively poor.
Yet, the present patent application people has found that through further investigation some new are used for painted compositions, they are that selectivity is little to the dyeing of cutin fiber, the influence of the various external environment that may be subjected to hair has good anti-patience again, wherein is used in combination with the cationic type direct dye of at least a following chemical formula known in the state of the art to a kind of specific cationic or amphoteric straight (connecing) dyeing polymer of major general.
Above-mentioned discovery is as basis of the present invention.
First purpose of the present invention is to obtain a kind of cutin fiber that is used for, human cutin fibre particularly, compositions as coloring hairs, wherein, in being suitable for painted medium, contain (i) at least a cationic type direct dye, its structure is shown in following chemical formula, and its characteristics are that it also contains (ii) at least a specific cationic or amphoteric straight (connecing) dyeing polymer.
(i) according to the present invention, employed cationic type direct dye has the chemical compound of following chemical formula (I), (II), (III) and (III '):
A) have the chemical compound of following chemical formula (I):
Figure C9910730500291
Wherein, D represent a nitrogen-atoms or-the CH base,
R 1With R 2Can be identical or different, represent a hydrogen atom; Energy by one-CN base ,-the OH base or-NH 2The C that base replaces 1-C 4Alkyl perhaps can form an optional oxygen or the nitrogen of containing with carbon atom in the phenyl ring, and can be by one or more C 1-C 4The heterocycle that alkyl replaced; 4 '-aminophenyl,
R 3With R ' 3Can be identical or different, represent a hydrogen atom or a halogen atom, be selected from chlorine, bromine, iodine and fluorine, a cyano group, C 1-C 4Alkoxyl or acetoxyl group,
X-represents an anion, preferentially is selected from chloride ion, methylsulfate and acetate,
A represents one to be selected from as following A 1-A 19The group of structure:
Figure C9910730500301
Figure C9910730500311
Wherein, R 4The C that represents an energy to be replaced by hydroxyl 1-C 4Alkyl, R 5Represent a C 1-C 4Alkoxyl, condition are D representative-CH, and A represents A 4Or A 13, and R 3Be different from alkoxyl, so R 1With R 2Can not hydrogen atom simultaneously;
B) have the chemical compound of following chemical formula (II):
Figure C9910730500312
Wherein, R 6Represent a hydrogen atom or C 1-C 4Alkyl,
R 7Represent a hydrogen atom; Energy quilt-CN base or the amino alkyl that replaces, 4 '-aminophenyl or and R 6Form an optional oxygen and/or the nitrogen of containing together, and can be by C 1-C 4The heterocycle that alkyl replaces,
R 8With R 9Can be identical or different, represent a hydrogen atom, a halogen atom, as bromine, chlorine, iodine or fluorine, a C 1-C 4Alkyl or C 1-C 4Alkoxyl, one-CN base,
X-represents an anion, preferentially is selected from chloride ion, methylsulfate and acetate,
B represents a group that is selected from as following B1-B6 structure:
R wherein 10Represent a C 1-C 4Alkyl, R 11With R 12Can be identical or different, represent a hydrogen atom or a C 1-C 4Alkyl;
C) have the chemical compound of following chemical formula (III) and (III '):
Wherein, R 13Represent a hydrogen atom, a C 1-C 4Alkoxyl, a halogen atom, as bromine, chlorine, iodine or fluorine, and an amino,
R 14Represent a hydrogen atom, a C 1-C 4Alkyl, perhaps with a phenyl ring in carbon atom form one and optionally contain oxygen and/or by one or more C 1-C 4The heterocycle that alkyl replaced,
R 15Represent a hydrogen atom or halogen atom, as bromine, chlorine, iodine or fluorine,
R 16With R 17Can be identical or different, represent a hydrogen atom or C 1-C 4Alkyl,
D 1With D 2Can be identical or different, represent a nitrogen-atoms-CH base,
M=O or 1,
Yet, work as R 13Represent one unsubstituted when amino, D 1With D 2Represent one-CH base and m=O simultaneously,
X -Represent an anion, preferentially be selected from chloride ion, methylsulfate and acetate,
E represents one to be selected from as following E 1-E 8The group of structure:
Figure C9910730500331
R wherein 1Represent a C 1-C 4Alkyl;
As m=O and D 1When representing a nitrogen-atoms, E also can represent the group with following E9 structure:
Figure C9910730500341
Wherein R ' represents a C 1-C 4Alkyl;
Be applicable to that the cationic type direct dye with chemical formula (I), (II), (III) and (III ') in the colouring compositions of the present invention is a compound known, and in patent documentation WO 95/01772, WO 95/15144 and EP-A-0714954, introduce.
Be applicable in the cationic type direct dye in the colouring compositions of the present invention, enumerate the chemical compound that has as following (I1)-(I52) structure especially with chemical formula (I):
Figure C9910730500342
Figure C9910730500351
Figure C9910730500361
Figure C9910730500401
Figure C9910730500431
In above-mentioned chemical compound with (I1)-(I52) structure, especially preferably have (I1), (I2), (I14) and (I31) chemical compound of structure.
Be applicable to and can enumerate chemical compound especially in the cationic type direct dye in the colouring compositions of the present invention with (II1)-(II12) structure with chemical formula (II):
Figure C9910730500442
Figure C9910730500451
Figure C9910730500471
Be applicable to and can enumerate chemical compound especially in the cationic type direct dye in the colouring compositions of the present invention with (III1)-(III18) structure with chemical formula (III):
Figure C9910730500472
Figure C9910730500501
In above-mentioned chemical compound with (III1)-(III18) structure, especially preferably have (III4), (III5) and (III13) chemical compound of structure.
Be applicable in the cationic type direct dye in the colouring compositions of the present invention, can enumerate especially and have (III ' 1)-chemical compound of (III ' 3) structure with chemical formula (III '):
Figure C9910730500502
The used cationic type direct dye of the present invention accounts for the 0.001-10% (weight) of colouring compositions gross weight, preferably is about 0.005-5% (weight).
(ii) can in following material, choose applicable to cationic or amphoteric straight (connecing) dyeing polymer of the present invention:
1/ cellulosic cationic derivative except Polyquaternium 10;
The halogenide of 2/ dimethyldiallylammonium and (methyl) acrylic acid copolymer;
The halid copolymer and the homopolymer of 3/ methacryloxyethyl trimethyl ammonium;
4/ is selected from the polymer of the polyquaternary amine of following material;
Polymer with repetitive of following chemical formula (IV):
Polymer with repetitive of following chemical formula V:
Polymer with repetitive of following chemical formula (VI):
Figure C9910730500513
Wherein, p is the integer of 1-6, and D can not have group or representative-(CH 2) r-CO-, r wherein equals 4 or 7;
The unitary vinylpyrrolidone copolymers of 5/ cation type;
6/ their mixture.
The substantivity of the polymer that the present invention is used can (promptly acting on the ability on the hair) normally pass through Richard J.Crawford at Journal of the Society of Cosmetic Chemists, 1980,31-(5), the above (Red 80 acid staiies) of test determines of 273-278 page or leaf.
These substantive polymer also can be selected from the polymer of having put down in writing in the existing document, for example the 19th row of the page 4 among the patent documentation EP-A-0557203---and the 12nd page, the 14th row.
We also can use cationic cellulose derivative, for example the quaternised cellulose ether derivative of putting down in writing in patent documentation EP-A-0189935, the particularly polymer of " the Quatrisoft LM200 " of Union Carbide Corp's sale; These polymer similarly are defined as the quaternary ammonium of the hydroxy ethyl cellulose that reacts with the epoxide that is replaced by the lauryl dimethyl ammonium by CTFA dictionary (1993, the 5th edition), be referred to herein as " Polyquaternium 24 '.
The halid straight dyeing polymer of the homopolymerization type that uses as the present invention and the methacryloxyethyl trimethyl ammonium of copoly type, especially can enumerate as CTFA dictionary (1993, the 5th edition) " the Polyquaternium 37 '; " Polyquaternium 32 ' and " Polyquaternum 35 " of name, wherein " Polyquaternium 37 " are the commodity Salcare SC95 that All ied Colloids company sells, it is the cross-linked homopolymer that is scattered in poly-(chloride of methacryloxyethyl trimethyl ammonium) of 50% in the mineral oil, above-mentioned " Polyquaternium 32 " are the commodity SalcareSC92 that Allied Colloids company sells, it is to be dispersed in the acrylamide of 50% in the mineral oil and the cross-linked copolymer of methacryloxyethyl trimethyl ammonium (part by weight is 20/80), above-mentioned " Polyquaternium 35 " are the commodity Plex 7525L that Rohn GmbH limited company sells, and it is the metilsulfate of the copolymer of methacryl oxo ethyl trimethyl ammonium and methacryloxyethyl dimethyl acetyl ammonium.
The halogenide of the dimethyldiallylammonium that uses as the present invention and the straight dyeing polymer of (methyl) acrylic acid copolymer type, especially can enumerate the commodity Merquat 280 that Calgon company sells, it is chloride and acrylic acid copolymer (part by weight is 80/20) of diallyl dimethyl ammonium.
The straight dyeing polymer of the polyquaternary amine type that the present invention uses, the especially material that can be listed below:
The polymer of the repetitive that-patent documentation FR 2270846 describes with following chemical formula (IV):
Particularly its molecular weight (according to gel permeation chromatography) is about the polymer of 9500-9900;
The polymer of the repetitive that-patent documentation FR 2270846 describes with following chemical formula V:
Figure C9910730500531
Particularly its molecular weight (according to gel permeation chromatography) is 1200 polymer;
-patent documentation US 4157388, US 4390689, and US 4702906, the polymer of the repetitive with following chemical formula (VI) that US 4719282 describes:
Wherein, P represents the integer of a 1-6, and D can not have group or one-(CH 2) the r-CO base, wherein r equals 4 or 7.The molecular weight of this polymer more preferably is less than or equal to 50000 preferably less than 100000; This base polymer especially comprises the commodity that Miranol company sells, and reaches " Mirapol 175 " as " Mirapol A15 ", " MirapolAD1 ", " Mirapol AZ1 ".
The polymer that the present invention uses with cationic unitary vinyl pyrrolidone (PVP), especially can enumerate:
A) include the vinyl pyrrolidone polymer of dimethylaminoethyl acrylate methyl base amino-ethyl ester structure, in these polymer, can list:
The copolymer (20/80 part by weight) of-vinyl pyrrolidone and dimethylaminoethyl acrylate methyl base amino-ethyl ester, it is the commodity COPOLYMER 845 that I.S.P. company sells;
-by the copolymer of quaternised vinyl pyrrolidone of dithyl sulfate and dimethylaminoethyl acrylate methyl base amino-ethyl ester, they are commodity GAFQUAT734,755,755S and 755L that I.S.P. company sells;
The copolymer of-PVP and dimethylaminoethyl acrylate methyl base amino-ethyl ester and hydrophilic polyurethane, they are the commodity PECOGEL GC-310 of U.C.I.B company sale or the commodity AQUAMERE C 1031 and C 1511 that BLAGDEN CHEMICALS company sells;
-PVP and dimethylaminoethyl acrylate methyl base amino-ethyl ester/C 8-C 16Quaternised or the not quaternised copolymer of alkene, they are commodity GANEX ACP 1050-1057,1062-1069,1079-1086 that I.S.P company sells;
The commodity GAFFIX 713 that-ISP company sells, i.e. the copolymer of PVP and dimethylaminoethyl acrylate methyl base amino-ethyl ester and caprolactam,
B) include the polymer of the unitary vinyl pyrrolidone of Methacrylamide oxypropyl trimethyl amine (M.A.P.T.A.C), in these polymer, can list:
Commodity GAFQUAT ACP 1011 and GAFQUAT HS 100, the i.e. copolymer of vinyl pyrrolidone and M.A.P.T.A.C that-ISP company sells.
C) include the polymer of the vinyl pyrrolidone of methyl ethylene imidazoline structure, in these polymer, can list:
Commodity LUVIQUAT FC 370, FC 550, FC 905, HM 552 that-B.A.S.F company sells, i.e. the muriatic copolymer of PVP/ methyl ethylene imidazoline,
The commodity LUVIQUAT 8155 that-B.A.S.F company sells, the i.e. copolymer of the chloride/vinyl imidazole of PVP/ methyl ethylene imidazoline;
The commodity LUVIQUAT MS 370 that-B.A.S.F company sells, the i.e. metilsulfate of PVP/ methyl ethylene imidazoline.
The above-mentioned straight dyeing polymer (ii) content in colouring compositions of the present invention accounts for the 0.01-10% (weight) of this colouring compositions gross weight, is preferably 0.1-5% (weight).
Be applicable to painted medium (or carrier) the normally water or the mixture of water and at least a organic solvent, organic solvent is used for dissolving those at the insufficient dissolved chemical compound of water.As the example of organic solvent, can enumerate C 1-C 4Lower alcohol, as ethanol and isopropyl alcohol; Aromatic alcohol, as benzyl alcohol or phenyl phenol, with and the mixture of similar substance and they.
Above-mentioned solvent accounts for the 1-40% (weight) of colouring compositions gross weight, preferably is about 5-30% (weight).
The pH value of colouring compositions is about 2-11 usually according to the present invention, preferably is about 5-10.Usually available acidulant or the basifier that is suitable for dyeing keratinous fibres is adjusted to required pH value.
As acidulant, can list, for example mineral acid or organic acid, example hydrochloric acid, orthophosphoric acid, sulphuric acid, carboxylic acid are as acetic acid, tartaric acid, citric acid, lactic acid, sulfonic acid.
As basifier, can list, for example ammonia, alkali carbonate, alkanolamine, as monoethanolamine, diethanolamine and triethanolamine and derivant thereof, sodium hydroxide or potassium hydroxide and chemical compound with following chemical formula (VII):
Figure C9910730500551
Wherein, W represents the acrylic or a C that may be replaced by hydroxyl 1-C 6Alkyl; R 18, R 19, R 20With R 21Can be identical or different, represent a hydrogen atom, C 1-C 6Alkyl or C 1-C 6Hydroxyalkyl.
In addition, except aforementioned cationic type direct dye (i), colouring compositions of the present invention also contains one or more additional direct dyess, for example optional self-nitro phenenyl dyestuff, anthraquinone dye, naphthoquinone dyestuff, triarylmethane dyes, Xanthine dyestuff, non-anion azo dye.
When being used for oxidising dyeing, except cationic type direct dye (i), colouring compositions of the present invention can also contain one or the polyoxy base material, for example optionally be used in the oxidation base material of oxidising dyeing, especially can be selected from p-phenylenediamine (PPD), diphenyl Alkylenediamine, para-aminophenol, o-aminophenol and heterocycle base material from tradition.
When being used for above-mentioned one or more oxidation base materials, its consumption preferably occupies the 0.0005-12% (weight) of colouring compositions gross weight approximately, preferably is about 0.005-6% (weight).
When as oxidising dyeing, except cationic type direct dye (i) and straight dyeing polymer (ii) reach the oxidation base material, colouring compositions of the present invention can also contain one or more colour formers, formed color or make it be rich in gloss when being used for improve using cationic type direct dye (i) with the oxidation base material.
According to the present invention, the colour former that tradition is used in the used optional comfortable oxidising dyeing of the colour former field in the colouring compositions especially can be selected from m-diaminobenzene., m-aminophenol, Resorcino and heterocycle colour former.
When using above-mentioned one or more colour formers, its consumption accounts for the 0.0001-10% (weight) of colouring compositions gross weight, preferably is about 0.005-5% (weight).
Colouring compositions of the present invention can also contain the various additives that tradition is used in the hair dyeing field, for example antioxidant, penetrating agent, sequestering agent, perfume, buffer agent, dispersant, surfactant, film former, ceramide, antiseptic, lightscreening agent, opacifier.
Certainly, those skilled in the art note and select those optional chemical compounds, make it can or can not change the inherent good characteristic of colouring compositions of the present invention basically.
According to the present invention, colouring compositions can be made different forms, and for example liquid, shampoo, cream, gel or other is applicable to the painted form of cutin fiber, especially human hair.Shampoo preferably wherein.
When (ii) being used in combination in the compositions of oxidising dyeing with straight dyeing polymer, (one or more oxidation base materials have wherein been used to cationic type direct dye of the present invention (i), and one or more colour formers), perhaps with their in conjunction with in the compositions of direct staining that is used to form the desalination tone time, colouring compositions so of the present invention just also contains at least a oxidant, for example can be selected from hydrogen peroxide, urea peroxide, alkali metal bromate, persalt such as perborate and persulfate, and enzyme such as peroxidase, laccase and have the oxidoreductase of two electronics.Preferably select hydrogen peroxide or enzyme for use.
Second purpose of the present invention is to implement cutin fiber with aforesaid colouring compositions, particularly the painted method of human hair.
First embodiment of colouring method according to the present invention is coated at least a above-mentioned colouring compositions on the fiber, and makes it have time enough to form desirable dyeing, flushing then, and optional shampoo is washed, and washes after drying once more.
On cutin fiber, can form normally 3-60 minute required time of coloration, be preferably 5-40 minute.
Second embodiment according to colouring method of the present invention is coated at least a above-mentioned colouring compositions on the fiber, and makes it have time enough to form required dyeing, but do not need final flushing process.
According to a special embodiment of this colouring method, and when containing at least a oxidation base material and at least a oxidant in the colouring compositions of the present invention, this colouring method also comprises the process in early stage of a compositions preserve separately that institute's desire is used.On the one hand, wherein in being applicable to painted medium, a kind of compositions (A1) contains at least a for example aforesaid cationic type direct dye (i) and at least a oxidation base material; On the other hand, wherein in being applicable to painted medium, a kind of compositions (B1) contains at least a oxidant, before the enforcement coating, in advance above-mentioned two kinds of compositionss are mixed mutually, and this mixture is coated on the cutin fiber, contain for example above-mentioned cationic or amphoteric straight dyeing polymer in above-mentioned composition (A1) or the compositions (B1).
According to another special embodiment of this colouring method, and when containing at least a oxidant in the colouring compositions of the present invention, this colouring method also comprises the process in early stage of a compositions preserve separately that institute's desire is used so.On the one hand, wherein in being applicable to painted medium, a kind of compositions (A2) contains at least a for example above-mentioned cationic type direct dye (i); On the other hand, wherein in being applicable to painted medium, a kind of compositions (B2) contains at least a oxidant, before implementing coating, in advance above-mentioned two kinds of compositionss are mixed mutually, and this mixture is coated on the cutin fiber, contain above-mentioned cationic or amphoteric straight dyeing polymer in said composition (A2) or the compositions (B2).
Another object of the present invention provides one " kit " that the device of many lattice chamber be housed or the dyeing usefulness of many lattice chamber is housed, perhaps other device with many lattice chamber, above-mentioned composition (A1) or (A2) wherein is housed in first lattice chamber, and above-mentioned compositions (B1) or (B2) is housed in second lattice chamber.This device can be equipped with desirable mixture is coated onto parts on the hair.This class device is described in french patent document FR 2586913 by the present patent application people.
Following example is described in further detail the present invention, but does not limit protection scope of the present invention.
Example
The following colouring compositions of example 1 preparation:
Cationic type direct dye 0.125 gram with Formula I (2)
M-aminophenol 0.120 gram
5-N-beta-hydroxyethyl amino-2-methyl-phenol 0.125 gram
The direct staining polymer:
The commodity Merquat 280 that CALGON company sells, it is
The chloride of diallyl dimethyl ammonium and acrylic acid
Copolymer (80/20 part by weight) 1.0 gram M.A. *
Polyglycereol oleyl alcohol 4.0 grams with two mole of glycerin
Polyglycereol oleyl alcohol with four mole of glycerin wherein has 78%
Active substance (M.A.) 5.69 gram M.A. *
Oleic acid 3.0 grams
The oleyl amine (commodity that AKZO company sells with two moles of ethylene oxide
ETHOMEEN 012) 7.0 grams
Lauryl aminosuccinic acid diethylamino propyl diester, sodium salt,
(have 55% M.A.) 3.0 gram M.A. *
Oleyl alcohol 5.0 grams
Oleic diglycollic amide 12.0 grams
Propylene glycol 3.5 grams
Dipropylene glycol 0.5 gram
Monomethyl ether 9.0 grams of propylene glycol
Ethanol 7.0 grams
Between sodium sulfite (metabisulfite de sodium) saline solution
(having 35%M.A.) 0.455 gram M.A. *
Ammonium acetate 0.8 gram
Antioxidant, sequestering agent are an amount of
Perfume, protective agent is an amount of
20%NH 3Ammonia 10.0 gram
Annotate: M.A. *The expression active substance
In use, said composition is mixed mutually with the commensurability aqueous hydrogen peroxide solution with 20 volumetrical (6% weight).
The compositions of above-mentioned formation is coated on the tuft of the natural achromachia with 90% poliosis.After 30 minutes, wash a tuft of the hair of above-mentioned processing, and with common shampoo washing, dry then.
After above-mentioned processing, formed and had scarlet glossy light flavous Color.
The following colouring compositions of example 2 preparations:
Cationic type direct dye 0.09 gram with Formula I (14)
Straight dyeing polymer 1.0 gram M.A. with polyquaternary amine type of chemical formula (IV) *
Nonyl phenol 8.0 grams with nine moles of ethylene oxide
An amount of pH=9 of 2-amino-2-methyl propanol
Demineralized water is in right amount to 100 grams
Annotate: M.A. *The expression active substance
Above-mentioned composition is coated on the tuft of the natural achromachia with 90% poliosis, after 30 minutes, washes a tuft of the hair of above-mentioned processing, and with common shampoo washing, dry then.
After above-mentioned processing, form bright foxy Color.

Claims (30)

1、用于人体角质纤维的染色组合物，其中在适合于染色的介质中，含有(i)至少一种如下列化学式(I)、(II)、(III)、(III’)的阳离子型直接染料：1. A dyeing composition for human keratinous fibers, which contains (i) at least one cationic compound of the following chemical formulas (I), (II), (III), (III') in a medium suitable for dyeing Direct Dyes:
Figure C991073050002C1
Figure C991073050002C1
 化学式(I)中，其中，In chemical formula (I), wherein, D代表氮原子或-CH基，D represents nitrogen atom or -CH group, R1与R2可以相同或不同，代表氢原子；能被-CN基、-OH基或-NH2基取代的C1-C4烷基，或者可以与苯环中的碳原子形成任选含氧或氮的，并能被一个或多个C1-C4烷基所取代的杂环；4’-氨基苯基，R 1 and R 2 may be the same or different, and represent a hydrogen atom; a C 1 -C 4 alkyl group that can be substituted by -CN, -OH or -NH 2 , or can form an optional carbon atom with a benzene ring Oxygen- or nitrogen-containing heterocycles which can be substituted by one or more C 1 -C 4 alkyl groups; 4'-aminophenyl, R3与R’3可以相同或不同，代表氢原子或选自氯、溴、碘和氟的卤素原子，或氰基，C1-C4烷氧基或乙酰氧基，R 3 and R' 3 may be the same or different, representing a hydrogen atom or a halogen atom selected from chlorine, bromine, iodine and fluorine, or a cyano group, C 1 -C 4 alkoxy or acetoxy, X-代表阴离子，X - stands for anion, A代表选自如下述A1-A19结构的基团：A represents a group selected from the following A 1 -A 19 structures:
Figure C991073050003C1
Figure C991073050003C1
 式中的R4代表能被羟基取代的C1-C4烷基，R5代表C1-C4烷氧基，R 4 in the formula represents a C 1 -C 4 alkyl group that can be substituted by a hydroxyl group, R 5 represents a C 1 -C 4 alkoxy group, 条件是D代表-CH，A代表A4或A13，以及R3不同于烷氧基时，那么R1与R2不能同时是氢原子；The condition is that D represents -CH, A represents A 4 or A 13 , and R 3 is different from alkoxy, then R 1 and R 2 cannot be hydrogen atoms at the same time; 化学式(II)中，其中，In chemical formula (II), wherein, R6代表氢原子或C1-C4烷基，R 6 represents a hydrogen atom or a C 1 -C 4 alkyl group, R7代表氢原子、能被-CN基或氨基所取代的烷基、4’-氨基苯基或与R6一起形成任选含氧和/或氮的，并可以被C1-C4烷基取代的杂环，R 7 represents a hydrogen atom, an alkyl group that can be substituted by a -CN group or an amino group, 4'-aminophenyl, or together with R 6 forms a group that optionally contains oxygen and/or nitrogen, and can be replaced by a C 1 -C 4 alkane substituted heterocycles, R8与R9可以相同或不同，代表氢原子、选自溴、氯、碘或氟的卤素原子、C1-C4烷基或C1-C4烷氧基、-CN基，R 8 and R 9 may be the same or different, representing a hydrogen atom, a halogen atom selected from bromine, chlorine, iodine or fluorine, C 1 -C 4 alkyl or C 1 -C 4 alkoxy, -CN group, X-代表阴离子，X - stands for anion, B代表选自如下述B1-B6结构的基团：B represents a group selected from the following B 1 -B 6 structures: 式中的R10代表C1-C4烷基，R11与R12可以相同或不同，代表氢原子或C1-C4烷基；R 10 in the formula represents a C 1 -C 4 alkyl group, R 11 and R 12 may be the same or different, and represent a hydrogen atom or a C 1 -C 4 alkyl group;
Figure C991073050005C1
Figure C991073050005C1
 化学式(III)与(III’)中，其中In chemical formula (III) and (III'), wherein R13代表氢原子、C1-C4烷氧基、选自溴、氯、碘或氟的卤素原子，或氨基，R 13 represents a hydrogen atom, a C 1 -C 4 alkoxy group, a halogen atom selected from bromine, chlorine, iodine or fluorine, or an amino group, R14代表氢原子、C1-C4烷基、或者与苯环中的碳原子形成任选含氧和/或被一个或多个C1-C4烷基所取代的杂环，R 14 represents a hydrogen atom, a C 1 -C 4 alkyl group, or forms a heterocyclic ring optionally containing oxygen and/or substituted by one or more C 1 -C 4 alkyl groups with a carbon atom in the benzene ring, R15代表氢原子或选自溴、氯、碘或氟的卤素原子， R represents a hydrogen atom or a halogen atom selected from bromine, chlorine, iodine or fluorine, R16与R17可以相同或不同，代表氢原子或C1-C4烷基，R 16 and R 17 may be the same or different, representing a hydrogen atom or a C 1 -C 4 alkyl group, D1与D2可以相同或不同，代表氮原子或-CH基，D 1 and D 2 can be the same or different, representing a nitrogen atom or a -CH group, m＝0或1，m=0 or 1, 应注意，当R13代表未被取代的氨基时，D1与D2同时代表-CH基，而且m＝0，It should be noted that when R 13 represents an unsubstituted amino group, D 1 and D 2 represent a -CH group at the same time, and m=0, X-代表阴离子，X - stands for anion, E代表选自如下述E1-E8结构的基团：E represents a group selected from the following E1-E8 structures:
Figure C991073050005C2
Figure C991073050005C2
 式中的R′代表C1-C4烷基，R' in the formula represents a C 1 -C 4 alkyl group, 当m＝0，D1代表氮原子时，E还可以代表具有下述E9结构的基团：When m=0, D When representing a nitrogen atom, E can also represent a group with the following E9 structure:
Figure C991073050006C1
Figure C991073050006C1
 式中的R′代表C1-C4烷基；R' in the formula represents C 1 -C 4 alkyl; 或选自以下的化合物：or a compound selected from:
Figure C991073050006C2
Figure C991073050006C2
 上述组合物的特征在于其中还含有(ii)至少一种如下述的阳离子型或两性的直染聚合物；The above-mentioned composition is characterized in that it also contains (ii) at least one cationic or amphoteric direct dyeing polymer as follows; 1/除了聚季10外的纤维素阳离子型衍生物；1/ Cationic derivatives of cellulose other than polyquaternium 10; 2/二甲基二烯丙基铵的卤化物与(甲基)丙烯酸的共聚物；2/ Copolymer of dimethyl diallyl ammonium halide and (meth)acrylic acid; 3/甲基丙烯酰氧基乙基三甲基铵的卤化物的共聚物与均聚物；3/ Copolymers and homopolymers of halides of methacryloxyethyltrimethylammonium; 4/选自下列物质的聚季铵聚合物：4/ Polyquaternium polymers selected from the group consisting of: —具有如下化学式(IV)的重复单元的聚合物：- polymers having recurring units of formula (IV):
Figure C991073050007C1
Figure C991073050007C1
 —具有如下化学式(V)的重复单元的聚合物：- polymers having recurring units of formula (V): —具有如下化学式(VI)的重复单元的聚合物：- polymers having repeating units of formula (VI):
Figure C991073050007C3
Figure C991073050007C3
 式中的p是1-6的整数，D可以无基团或代表-(CH2)r-CO-，其中的r是等于4或7；In the formula, p is an integer of 1-6, and D can have no group or represent -(CH 2 ) r -CO-, where r is equal to 4 or 7; 5/含阳离子型单元的乙烯基吡咯烷酮的共聚物；5/ Copolymers of vinylpyrrolidone containing cationic units; 6/它们的混合物。6/ Mixtures thereof. 2、根据权利要求1所述的组合物，其特征在于具有化学式(I)的阳离子型直接染料选自具有如下(I1)-(I5)、(I7)-(I28)、(I30)-(I46)、(I48)-(I50)、(I52)-(I54)之一结构的化合物：2. The composition according to claim 1, characterized in that the cationic direct dyes of formula (I) are selected from the group consisting of (I1)-(I5), (I7)-(I28), (I30)-( Compounds with one of I46), (I48)-(I50), (I52)-(I54):
Figure C991073050010C1
Figure C991073050010C1
Figure C991073050013C1
Figure C991073050013C1
Figure C991073050016C1
Figure C991073050016C1
Figure C991073050018C1
Figure C991073050018C1
 3、根据权利要求2所述的组合物，其特征在于其中所述的阳离子型直接染料具有(I1)、(I2)、(I14)或(I31)结构。3. The composition according to claim 2, wherein said cationic direct dye has the structure (I1), (I2), (I14) or (I31). 4、根据权利要求1所述的组合物，其特征在于具有化学式(II)的阳离子型直接染料包括选自如下结构(II1)-(II3)、(II5)、(II6)、(II8)、(II10)-(II12)之一的化合物：4. The composition according to claim 1, characterized in that the cationic direct dyes of formula (II) are selected from the group consisting of the following structures (II1)-(II3), (II5), (II6), (II8), Compounds of one of (II10)-(II12):
Figure C991073050019C1
Figure C991073050019C1
Figure C991073050020C1
Figure C991073050020C1
 5、根据权利要求1所述的组合物，其特征在于具有化学式(III)的阳离子型直接染料选自具有下列结构(III1)-(III18)之一的化合物：5. The composition according to claim 1, characterized in that the cationic direct dyes of formula (III) are selected from compounds having one of the following structures (III 1 )-(III 18 ):
Figure C991073050021C1
Figure C991073050021C1
Figure C991073050022C1
Figure C991073050022C1
Figure C991073050023C1
Figure C991073050023C1
 6、根据权利要求5所述的组合物，其特征在于所述的具有化学式(III)的阳离子型直接染料选自具有结构(III4)、(III5)或(III13)的化合物。6. The composition according to claim 5, characterized in that the cationic direct dyes of formula (III) are selected from compounds of structure (III4), (III5) or (III13). 7、根据权利要求1的所述组合物，其特征在于所述的具有化学式(III’)的阳离子型直接染料选自具有结构(III’1)-(III’3)之一的化合物：7. The composition according to claim 1, characterized in that the cationic direct dyes of formula (III') are selected from compounds having one of the structures (III'1)-(III'3): 8、根据权利要求1所述的组合物，其中所述的X-代表的阴离子选自氯离子、甲基硫酸根或醋酸根。8. The composition according to claim 1, wherein said anion represented by X- is selected from chloride, methylsulfate or acetate. 9、根据权利要求1-8的任一项权利要求所述的组合物，其特征在于其中所述的具有化学式(I)、(II)、(III)或(III’)的一种或多种阳离子型直接染料占所述组合物总重量的0.001-10％重量。9. The composition according to any one of claims 1-8, wherein said one or more compounds of formula (I), (II), (III) or (III') A cationic direct dye comprises 0.001-10% by weight of the total weight of the composition. 10、根据权利要求9所述的组合物，其特征在于其中所述的具有化学式(I)、(II)、(III)或(III’)的一种或多种阳离子型直接染料的占所述组合物总重量的0.005-5％重量。10. The composition according to claim 9, wherein said one or more cationic direct dyes of formula (I), (II), (III) or (III') account for 0.005-5% by weight of the total weight of the composition. 11、根据权利要求中1-8的任一权利要求所述的组合物，其特征在于其中所述的纤维素直染聚合物是聚季24。11. The composition according to any one of claims 1-8, wherein said cellulose substantive polymer is polyquaternium-24. 12、根据权利要求1-8的中任一权利要求所述的组合物，其特征在于其中所述的(甲基)丙烯酸与二甲基二烯丙基铵的卤化物的共聚合物型的直染聚合物是二甲基二烯丙基铵的氯化物与丙烯酸按80/20重量比例的共聚物。12. The composition according to any one of claims 1-8, wherein said (meth)acrylic acid and dimethyldiallylammonium halide copolymer type The substantive polymer is an 80/20 weight ratio copolymer of dimethyldiallylammonium chloride and acrylic acid. 13、根据权利要求1-8的任一权利要求所述的组合物，其特征在于其中所述的甲基丙烯酰氧基乙基三甲基铵的卤化物的均聚物和共聚物型的直染聚合物选自分散于矿物油中的50％的甲基丙烯酰氧代乙基三甲基铵的氯化物的聚合物的交联均聚物，分散于矿物油中的50％的丙烯酰胺与甲基丙烯酰氧基乙基三甲基铵的氯化物按80/20重量比例的交联共聚物，甲基丙烯酰氧基乙基三甲基铵与甲基丙烯酰氧基乙基二甲基乙酰基铵的共聚物的甲基硫酸盐。13. The composition according to any one of claims 1-8, characterized in that the homopolymer and copolymer type of halide of methacryloxyethyltrimethylammonium The substantive polymer is selected from the cross-linked homopolymer of polymers of 50% methacryloyloxyethyltrimethylammonium chloride dispersed in mineral oil, 50% propylene dispersed in mineral oil Cross-linked copolymer of amide and chloride of methacryloxyethyltrimethylammonium 80/20 by weight, methacryloxyethyltrimethylammonium Copolymer of dimethyl acetyl ammonium methyl sulfate. 14、根据权利要求1-8的任一权利要求所述的组合物，其特征在于其中所述的含有阳离子型单元的乙烯基吡咯烷酮聚合物型的直染聚合物选自：14. The composition according to any one of claims 1-8, wherein said direct dyeing polymer of vinylpyrrolidone polymer type containing cationic units is selected from: a)具有甲基丙烯酸二甲基氨基乙基酯单元的乙烯基吡咯烷酮聚合物；a) vinylpyrrolidone polymers having dimethylaminoethyl methacrylate units; b)具有甲基丙烯酰氨基丙基三甲基铵单元的乙烯基吡咯烷酮聚合物；b) vinylpyrrolidone polymers with methacrylamidopropyltrimethylammonium units; c)具有甲基乙烯基咪唑啉单元的乙烯基吡咯烷酮的聚合物。c) Polymers of vinylpyrrolidone having methylvinylimidazoline units. 15、根据权利要求1所述的组合物，其特征在于其中所述的一种或多种直染聚合物(ii)占所述组合物总重量的0.01-10％重量。15. The composition according to claim 1, wherein said one or more substantive polymers (ii) account for 0.01-10% by weight of the total weight of said composition. 16、根据权利要求15所述的组合物，其特征在于其中所述的直染聚合物(ii)的含量占所述组合物总重量的0.1-5％重量。16. The composition according to claim 15, wherein the content of the direct dyeing polymer (ii) is 0.1-5% by weight of the total weight of the composition. 17、根据权利要求1-8的任一权利要求所述的组合物，其特征在于其中所述的适合于染色的介质或载体包括水或由水与至少一种有机溶剂组成的混合物。17. A composition according to any one of claims 1-8, wherein said medium or carrier suitable for dyeing comprises water or a mixture of water and at least one organic solvent. 18、根据权利要求1-8的任一权利要求所述的组合物，其特征在于其pH值为2-11。18. Composition according to any one of claims 1-8, characterized in that it has a pH of 2-11. 19、根据权利要求1的组合物，其特征在于该组合物用于氧化染色，其特征还在于其中含有一种或多种氧化基料，该氧化基料选自对苯二胺、二苯基亚烷基二胺、对氨基苯酚、邻氨基苯酚以及杂环基料。19. The composition according to claim 1, characterized in that it is used for oxidative dyeing, and in that it contains one or more oxidizing base materials selected from the group consisting of p-phenylenediamine, diphenyl Alkylenediamines, p-aminophenols, ortho-aminophenols and heterocyclic binders. 20、根据权利要求19所述的组合物，其特征在于其中所述的一种或多种氧化基料的占染色组合物总重量的0.0005-12％重量。20. The composition according to claim 19, wherein said one or more oxidized binders constitute 0.0005-12% by weight of the total weight of the dyeing composition. 21、根据权利要求20所述的组合物，其特征在于其中所述的氧化基料占染色组合物总重量的0.005-6％重量。21. The composition according to claim 20, wherein said oxidized binder accounts for 0.005-6% by weight of the total weight of the dyeing composition. 22、根据权利要求19-21中任一权利要求所述的组合物，其特征在于其中还含有一种或多种发色剂，该发色剂选自间苯二胺、间氨基苯酚、间二苯酚以及杂环发色剂。22. The composition according to any one of claims 19-21, characterized in that it also contains one or more chromogenic agents selected from the group consisting of m-phenylenediamine, m-aminophenol, m- Diphenols and heterocyclic chromogens. 23、根据权利要求22所述的组合物，其特征在于其中所述的一种或多种发色剂占染色组合物总重量的0.0001-10％重量。23. The composition according to claim 22, wherein said one or more color formers constitute 0.0001-10% by weight of the total weight of the dyeing composition. 24、根据权利要求23所述的组合物，其特征其中所述的一种或多种发色剂占染色组合物总重量的0.005-5％重量。24. The composition according to claim 23, wherein said one or more color formers constitute 0.005-5% by weight of the total weight of the dyeing composition. 25、根据权利要求1-8的一权利要求所述的组合物，其特征在于该组合物用于氧化染色或淡化直接染色，其特征还在于该组合物还含有至少一种氧化剂。25. Composition according to one of claims 1-8, characterized in that it is used for oxidative dyeing or lightening of direct dyeing, and in that it also contains at least one oxidizing agent. 26、一种对人体的角质纤维的染色方法，其特征在于将上述权利要求1-25中任一权利要求所述的至少一种染色组合物涂敷在所述纤维上，并用足够的时间使其形成所希望的染色效果，然后冲洗，并任选地用洗发剂洗涤，接着再次冲洗，最后干燥。26. A method for dyeing keratinous fibers of the human body, characterized in that at least one dyeing composition according to any one of claims 1-25 is applied to the fibers, and a sufficient time is used to apply It develops the desired color effect, is then rinsed, and optionally shampooed, rinsed again, and finally dried. 27、一种对人体的角质纤维的染色方法，其特征在于将上述权利要求1-25中任一权利要求所述的至少一种染色组合物涂敷在所述纤维上，并用足够的时间使其形成所希望的染色，但不需要最终的冲洗过程。27. A method for dyeing keratinous fibers of the human body, characterized in that at least one dyeing composition according to any one of claims 1-25 is applied to the fibers, and a sufficient time is used to apply It forms the desired stain, but does not require a final rinse process. 28、一种对人体的角质纤维的染色方法，其特征在于该方法包括将欲用的组合物分别存放的前期过程，一方面，其中在适用于染色的介质中，一种组合物(A1)含有至少一种在权利要求1或2中所限定的阳离子型直接染料(i)与至少一种氧化基料，另一方面，其中在适用于染色的介质中，一种组合物(B1)含有至少一种氧化剂，然后，在实施涂敷之前，预先将(A1)和(B1)两种组合物相混合，并将该混合物涂敷在角质纤维上，该组合物(A1)或组合物(B1)中含有权利要求1或2所限定的直染聚合物(ii)。28. A method for dyeing keratinous fibers of the human body, characterized in that the method includes a preliminary process of separately storing the compositions to be used, on the one hand, in a medium suitable for dyeing, a composition (A1) Containing at least one cationic direct dye (i) as defined in claim 1 or 2 and at least one oxidative binder, wherein, in another aspect, in a medium suitable for dyeing, a composition (B1) contains At least one oxidizing agent, then, before the application, the two compositions (A1) and (B1) are mixed in advance, and the mixture is applied on the keratinous fibers, the composition (A1) or the composition ( B1) contains the direct dyeing polymer (ii) as defined in claim 1 or 2. 29、一种对人体的角质纤维的染色方法，其特征在于该方法还包括将欲用的组合物分别存放的前期过程，一方面，其中在适用于染色的介质中，一种组合物(A2)含有至少一种在权利要求1或2所限定的阳离子型直接染料(i)，另一方面，在适用于染色的介质中，一种组合物(B2)含有至少一种氧化物，在实施涂敷之前预先将上述组合物(A2)和组合物(B2)相混合，然后将该混合物涂敷在角质纤维上，上述组合物(A2)或组合物(B2)中含有前述权利要求1或2所限定的直染聚合物(ii)。29. A method for dyeing keratinous fibers of the human body, characterized in that the method also includes a preliminary process of separately storing the compositions to be used. On the one hand, in a medium suitable for dyeing, a composition (A2 ) containing at least one cationic direct dye (i) as defined in claim 1 or 2, on the other hand, in a medium suitable for dyeing, a composition (B2) containing at least one oxide, in the implementation Before coating, the above composition (A 2 ) and composition (B 2 ) are mixed in advance, and then the mixture is applied on the keratinous fibers, and the above composition (A2) or composition (B2) contains the above claim The direct dyeing polymer (ii) as defined in 1 or 2. 30、装有多格室的装置或装有多格室的染色用“用具包”，其特征在于第一个格室中装有根据权利要求28或29的方法中所限定的组合物(A1)或(A2)，而在第二个格室中装有根据权利要求28或29的方法中所限定的组合物(B1)或(B2)。30. A multi-compartment device or a multi-compartment "kit" for dyeing, characterized in that the composition as defined in the method according to claim 28 or 29 is contained in the first compartment (A1 ) or (A2), while the second compartment contains the composition (B1) or (B2) as defined in the method according to claim 28 or 29.
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